PLASTICIZER COMPOSITION, RESIN COMPOSITION, AND PREPARATION METHODS THEREFOR

Description

TECHNICAL FIELD

Cross-reference to Related Applications

[0001] This application claims the benefit of Korean Patent Application Nos. 10-2015-0021783, filed on February 12, 2015, 10-2015-0041794, filed on March 25, 2015, 10-2015-0113875, filed on August 12, 2015, and 10-2015-0144889, filed on October 16, 2015, in the Korean Intellectual Property Office.

Technical Field

[0002] The present invention relates to a plasticizer composition and a resin composition, and a preparation method thereof.

BACKGROUND ART

[0003] Typically, with respect to a plasticizer, alcohol reacts with polycarboxylic acid, such as phthalic acid and adipic acid, to form an ester corresponding thereto. Also, in consideration of domestic and foreign regulations limiting phthalate-based plasticizers that are harmful to human body, research into plasticizer compositions, which may replace phthalate-based plasticizers such as terephthalate-based plasticizers, adipate-based plasticizers, and other polymer-based plasticizers, has continued.

[0004] In order to manufacture flooring materials, wallpaper, sheet products, an appropriate plasticizer must be used in consideration of discoloration, migration, and processability. A plasticizer, a filler, a stabilizer, a viscosity reducing agent, a dispersant, an antifoaming agent, and a foaming agent are mixed with a PVC resin according to properties required by industry in various use areas, for example, tensile strength, elongation rate, light resistance, migration, gelling property, or processability.

[0005] For example, in a case in which inexpensive dioctyl terephthalate is used among plasticizer compositions that are applicable to PVC, its viscosity is high, the absorption rate of the plasticizer is relatively low, and migration is also not good.

[0006] Thus, there is a continuous need to research into techniques by which a product better than the dioctyl terephthalate or a novel composition product including dioctyl terephthalate is developed and optimally used as a plasticizer for a vinyl chloride-based resin.

DISCLOSURE OF THE INVENTION

TECHNICAL PROBLEM

[0007] As a result of continuous research into plasticizers, the present inventors found a plasticizer composition which may improve poor physical properties that have been ascribed to structural limitations, thereby leading to the completion of the present invention.

[0008] The present invention provides a plasticizer which may improve physical properties, such as plasticizing efficiency, migration, and gelling property, required for a sheet formulation when used as a plasticizer of a resin composition, a preparation method thereof, and a resin composition including the plasticizer.

TECHNICAL SOLUTION

[0009] According to an aspect of the present invention, there is provided a plasticizer composition including a terephthalate-based material; and a Citrate-based material, wherein a weight ratio of the terephthalate-based material to the Citrate-based material is in a range of 8 : 2 to 6 : 4,
wherein the Citrate-based material is one in which an acetyl group is not included, and
wherein the terephthalate-based material and the Citrate-based material are, respectively,

(a) di(2-ethylhexyl)terephthalate (DEHTP or DOTP) and triisobutyl citrate (TiBC), or

(b) diisononyl terephthalate (DINTP) and tributyl citrate (TBC), or

(c) diisononyl terephthalate (DINTP) and triisobutyl citrate (TiBC).

[0010] The plasticizer composition may further include an epoxidized oil.

[0011] The epoxidized oil may be included in an amount of 1 parts by weight to 100 parts by weight based on 100 parts by weight of the plasticizer composition.

[0012] The epoxidized oil may include at least one selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid ester, epoxidized oleic acid ester, epoxidized tall oil, and epoxidized linoleic acid ester.

[0013] According to another aspect of the present invention, there is provided a method of preparing a plasticizer composition including preparing a terephthalate-based material and a Citrate-based material as defined above and obtaining a plasticizer compound by blending the terephthalate-based material and the Citrate-based material in a weight ratio of 8 : 2 to 6 : 4.

[0014] According to another aspect of the present invention, there is provided a resin composition including 100 parts by weight of a resin; and 5 parts by weight to 150 parts by weight of the plasticizer composition as defined above.

[0015] The resin may include at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and a thermoplastic elastomer.

[0016] The resin composition may be a material of at least one product selected from the group consisting of electric wires, flooring materials, automotive interior materials, films, sheets, wallpaper, and tubes.

ADVANTAGEOUS EFFECTS

[0017] A plasticizer composition according to an embodiment of the present invention may provide excellent physical properties, such as migration resistance and volatility resistance, as well as excellent plasticizing efficiency, tensile strength, and elongation rate when used in a resin composition.

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The following drawings attached to the specification illustrate preferred examples of the present invention by example, and serve to enable technical concepts of the present invention to be further understood together with detailed description of the invention given below, and therefore the present invention should not be interpreted only with matters in such drawings.

FIG. 1 is an image illustrating the results of heat resistance tests for resins including plasticizer compositions according to the present invention;

FIG. 2 is an image illustrating the results of heat resistance tests for the resins including the plasticizer compositions according to the present invention; and

FIG. 3 is an image illustrating the results of thermal stability tests for the resins including the plasticizer compositions according to the present invention.

MODE FOR CARRYING OUT THE INVENTION

[0019] Hereinafter, the present invention will be described in detail.

[0020] First, the present invention has technical features that provide a plasticizer composition which may improve poor physical properties that have been ascribed to structural limitations.

[0021] Herein, the terephthalate-based material and the Citrate-based material in the plasticizer composition are included in a weight ratio of 8 : 2 to 6 : 4.

[0022] The plasticizer composition including the terephthalate-based material and the Citrate-based material may further include epoxidized oil. The epoxidized oil may be included in an amount of 1 parts by weight to 100 parts by weight, preferably, 1 parts by weight to 80 parts by weight, based on 100 parts by weight of the plasticizer composition.

[0023] With respect to the mixed plasticizer composition of the terephthalate-based material and the Citrate-based material, heat resistance properties among various physical properties may be relatively poor, and the poor heat resistance properties may be compensated by further including the epoxidized oil. In a case in which the amount of the epoxidized oil is greater than 100 parts by weight, physical properties, such as migration resistance, volatility resistance, or tensile strength, of the mixed plasticizer composition may be relatively deteriorated, and, in a case in which the amount of the epoxidized oil included is less than 1 parts by weight, the poor heat resistance properties may not be compensated. However, if the epoxidized oil is included in the range of 1 parts by weight to 80 parts by weight, properties such as heat resistance, tensile strength, or volatility resistance may be optimized. But, the plasticizer composition can have excellent properties unless the epoxidized oil is greater than 100 parts by weight.

[0024] Examples of the epoxidized oil may be epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid, epoxidized oleic acid, epoxidized tall oil, epoxidized linoleic acid, or a mixture thereof. For example, the epoxidized soybean oil (ESO) or the epoxidized linseed oil (ELO) may be used, but the present invention is not limited thereto.

[0025] A blending method may be used as a method of preparing the plasticizer composition in the present invention, wherein the blending method, for example, is as follows:

[0026] A terephthalate-based material and a Citrate-based material are prepared, and the plasticizer composition may be prepared by blending the terephthalate-based material and the Citrate-based material identified above in a weight ratio of 8:2 to 6:4,

[0027] The plasticizer composition thus prepared may provide a resin composition that is effective to compound formulation, sheet formulation, and plastisol formulation by being included in an amount of 5 parts by weight to 150 parts by weight, 40 parts by weight to 100 parts by weight, or 40 parts by weight to 50 parts by weight based on 100 parts by weight of a resin selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and a thermoplastic elastomer.

[0028] For example, the plasticizer composition may be used in the manufacture of electric wires, flooring materials, automotive interior materials, films, sheets, wallpaper, or tubes.

Examples

[0029] Hereinafter, the present invention will be described in detail according to specific examples. The invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present invention to those skilled in the art.

Preparation Example 1: Preparation of DOTP

[0030] 498.0 g of purified terephthalic acid (TPA), 1,170 g of 2-ethylhexyl alcohol (2-EH) (molar ratio of TPA:2-EH=1.0:3.0), and 1.54 g (0.31 part by weight based on 100 parts by weight of the TPA) of a titanium-based catalyst (tetra isopropyl titanate, TIPT) as a catalyst were put in a 3 liter, four-neck reactor equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, and a stirrer, and the temperature was slowly increased to about 170°C. The generation of water was initiated at about 170°C, and an esterification reaction was conducted for about 4.5 hours while continuously introducing nitrogen gas at a reaction temperature of about 220°C under an atmospheric pressure condition. The reaction was terminated when an acid value reached 0.01.

[0031] After the completion of the reaction, distillation extraction was performed for 0.5 hours to 4 hours under reduced pressure in order to remove unreacted raw materials. Steam extraction was performed for 0.5 hours to 3 hours under reduced pressure using steam in order to remove the unreacted raw materials below a predetermined amount level. A temperature of a reaction solution was cooled to about 90°C to perform a neutralization treatment using an alkaline solution. In addition, washing may also be performed and thereafter, water was removed by dehydrating the reaction solution. Filter media were introduced into the dehydrated reaction solution and stirred for a predetermined time. Then, the solution was filtered to finally obtain 1,326.7 g (yield: 99.0%) of di-2-ethylhexyl terephthalate.

Preparation Example 2: Preparation of DINTP

[0032] DINTP was prepared in the same manner as in Preparation Example 1 except that isononyl alcohol was used instead of using 2-ethylhexyl alcohol during the esterification reaction.

Preparation Example 3: Preparation of DOTP/BOTP/DBTP mixture (First Mixture) (GL 500)

[0033] 2,000 g of dioctyl terephthalate obtained in Preparation Example 1 and 340 g of n-butanol (17 parts by weight based on 100 parts by weight of the DOTP) were introduced into a reactor equipped with a stirrer, a condenser, and a decanter, and a transesterification reaction was carried out at a reaction temperature of 160°C for 2 hours under a nitrogen atmosphere to obtain an ester plasticizer composition including 4.0 wt% of dibutyl terephthalate (DBTP), 35.0 wt% of butylisononyl terephthalate (BINTP), and 61.0 wt% of diisononyl terephthalate (DINTP).

[0034] Mixed distillation of the reaction product was conducted to remove butanol and 2-ethylhexyl alcohol and to finally prepare a first mixture.

Preparation Example 4: Preparation of DXNTP/OIHTP/DOTP mixture (Third Mixture) (GL 100)

[0035] 498.0 g of purified terephthalic acid (TPA), 975 g of 2-ethylhexyl alcohol (2-EH) (molar ratio of TPA:2-EH=1.0:2.5), 216.5 g of isononyl alcohol (INA) (molar ratio of TPA:INA=1.0:0.5), and a titanium-based catalyst (tetra isopropyl titanate, TIPT) as a catalyst were put in a 3 liter, four-neck reactor equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, and a stirrer, and the temperature was slowly increased to about 170°C. The generation of water was initiated at about 170°C, and an esterification reaction was conducted for about 4.5 hours while continuously introducing nitrogen gas at a reaction temperature of about 220°C under an atmospheric pressure condition. The reaction was terminated when an acid value reached 0.01.

[0036] After the completion of the reaction, distillation extraction was performed for 0.5 hours to 4 hours under reduced pressure in order to remove unreacted raw materials. Steam extraction was performed for 0.5 hours to 3 hours under reduced pressure using steam in order to remove the unreacted raw materials below a predetermined amount level. A temperature of a reaction solution was cooled to about 90°C to perform a neutralization treatment using an alkaline solution. In addition, washing may also be performed and thereafter, water was removed by dehydrating the reaction solution. Filter media were introduced into the dehydrated reaction solution and stirred for a predetermined time. Then, the solution was filtered to finally obtain a third mixture.

Preparation Example 5: Preparation of TBC

[0037] 706 g (yield: 98%) of tributyl citrate was finally obtained by using 384 g of citric acid and 580 g of butanol as reaction raw materials.

Preparation Example 6: Preparation of TOC

[0038] 1,029 g (yield: 98%) of tri-2-ethylhexyl citrate was finally obtained by using 384 g of citric acid and 1,014 g of 2-ethylhexanol as reaction raw materials.

Preparation Example 7: Preparation of TPC

[0039] 796 g (yield: 98%) of tripentyl citrate was finally obtained by using 384 g of citric acid and 688 g of 1-pentanol as reaction raw materials.

Preparation Example 8: Preparation of THC

[0040] 878 g (yield: 98%) of trihexyl citrate was finally obtained by using 384 g of citric acid and 797 g of n-hexanol as reaction raw materials.

Preparation Example 9: Preparation of TiBC

[0041] 706 g (yield: 98%) of triisobutyl citrate was finally obtained by using 384 g of citric acid and 580 g of isobutanol as reaction raw materials.

Preparation Example 10: Preparation of TiNC

[0042] 1,111 g (yield: 98%) of triisobutyl citrate was finally obtained by using 384 g of citric acid and 1,123 g of isononanol as reaction raw materials.

Preparation Example 11: Preparation of BOC-A

[0043] A transesterification reaction was carried out by using 1,000 g of the TOC prepared in Preparation Example 6 and 300 g of n-butanol as reaction raw materials, and 840 g of butyloctyl citrate was finally obtained. For reference, the product is a composition, wherein main components are BOC bonded to two butyl groups, BOC bonded to one butyl group, and TOC not bonded to a butyl group, which were categorized by the alkyl group bonded to three ester groups of the citrate compound, and weight ratios of the main components were about 20%, 50%, and 30%, respectively.

Preparation Example 12: Preparation of BOC-B

[0044] A transesterification reaction was carried out by using 1,000 g of the TOC prepared in Preparation Example 6 and 150 g of n-butanol as reaction raw materials, and 940 g of butyloctyl citrate was finally obtained. For reference, the product is a composition, wherein main components are BOC bonded to two butyl groups, BOC bonded to one butyl group, and TOC not bonded to a butyl group, which were categorized by the alkyl group bonded to three ester groups of the citrate compound, and weight ratios of the main components were about 10%, 40%, and 50%, respectively.

[0045] Plasticizer compositions of Examples 1 to 17 were prepared by mixing the materials prepared in Preparation Examples 1 to 12, and the compositions are summarized in the following Tables 1 to 5. The plasticiser compositions for which the mixing ratio is outside the range 8 : 2 to 6 : 4 or which involve different combinations of terephthalate-based materials and Citrate-based materials are recited for comparison only. Examples 5-1, 5-2, 9-1, 9-2, 11-1 and 11-2 are thus according to the invention. Physical properties of the plasticizer compositions were evaluated according to the following test items.

[Table 1]

	Terephthalate-based material	Citrate-based material	Mixing weight ratio
Example 1-1	Preparation Example 1 (DOTP)	Preparation Example 5 (TBC)	95:5
Example 1-2			7:3
Example 1-3			5:5
Example 1-4			3:7
Example 1-5			1:9
Example 2-1		Preparation Example 6 (TOC)	95:5
Example 2-2			7:3
Example 2-3			5:5
Example 2-4			3:7
Example 2-5			1:9
Example 3-1		Preparation Example 7 (TPC)	9:1
Example 3-2			7:3
Example 3-3			5:5
Example 4-1		Preparation Example 8 (THC)	9:1
Example 4-2			7:3
Example 4-3			5:5
Example 5-1		Preparation Example 9 (TiBC)	8:2
Example 5-2			6:4
Example 5-3			4:6
Example 5-4			2:8
Example 6-1		Preparation Example 10 (TiNC)	9:1
Example 6-2			7:3
Example 6-3			5:5
Example 6-4			3:7
Example 6-5			1:9
Example 7-1		Preparation Example 11 (BOC-A)	85:15
Example 7-2			7:3
Example 7-3			6:4
Example 8-1		Preparation Example 12 (BOC-B)	85:15
Example 8-2			7:3
Example 8-3			6:4

[Table 2]

	Terephthalate-based material	Citrate-based material	Mixing weight ratio
Example 9-1	Preparation Example 2 (DINTP)	Preparation Example 5 (TBC)	8:2
Example 9-2			6:4
Example 9-3			4:6
Example 9-4			2:8
Example 10-1		Preparation Example 6 (TOC)	8:2
Example 10-2			6:4
Example 10-3			4:6
Example 10-4			2:8
Example 11-1		Preparation Example 9 (TiBC)	8:2
Example 11-2			6:4
Example 11-3			4:6
Example 11-4			2:8

[Table 3]

	Terephthalate-based material	Citrate-based material	Mixing weight ratio
Example 12-1	Preparation Example 3	Preparation Example 11 (BOC-A)	85:15
Example 12-2			7:3
Example 12-3			6:4
Example 13-1		Preparation Example 12 (BOC-B)	85:15
Example 13-2			7:3
Example 13-3			6:4

[Table 4]

	Terephthalate-based material	Citrate-based material	Mixing weight ratio
Example 14-1	Preparation Example 4	Preparation Example 5 (TBC)	95:5
Example 14-2			7:3
Example 14-3			5:5
Example 14-4			1:9
Example 15-1		Preparation Example 6 (TOC)	7:3

[Table 5]

	Terephthalate-based material	Citrate-based material	Epoxidized oil	Mixing weight ratio
Example 16-1	Preparation Example 1 (DOTP)	Preparation Example 5 (TBC)	ESO	(3:5) :2
Example 16-2				(6:3):1
Example 16-3				(6:2):2
Example 16-4				(5:3):2
Example 16-5				(4:4):2
Example 17-1		Preparation Example 6 (TOC)		(3:3) :4
Example 17-2				(4:3):3
Example 17-3				(5:3):2

<Test Items>

Hardness Measurement

[0046] Shore hardness (3T, 10s) was measured at 25°C in accordance with ASTM D2240.

Tensile Strength Measurement

[0047] A breaking point of a specimen was measured after pulling the specimen at a cross-head speed of 200 mm/min (1T) using a test instrument, U.T.M (4466, Instron) by the method of ASTM D638. The tensile strength was calculated as follows.

Elongation Rate Measurement

[0048] A breaking point of a specimen was measured after pulling the specimen at a cross-head speed of 200 mm/min (IT) using the U.T.M by the method of ASTM D638, and the elongation rate was calculated as follows.

Migration Loss Measurement

[0049] A specimen having a thickness of 2 mm or more was obtained in accordance with KSM-3156. PS plates were respectively attached on both sides of the specimen, and the weight of 1 kgf/cm² was then applied thereto. The specimen was left standing for 72 hours in a hot air circulating oven (80°C), and cooled at room temperature for 4 hours. Thereafter, the PS plates attached to the both sides of the specimen were removed. Then, weights of the specimen before and after being left standing in the oven were measured, and migration loss was calculated by the following equation.

Volatile Loss Measurement

[0050] The specimen thus prepared was heated at 80°C for 72 hours, and the weight of the specimen was measured.

Stress Test

[0051] After the specimen, in a state of being bent, was left standing for a predetermined time at room temperature, degree of migration was observed and the degree was expressed as a numerical value. Characteristics were better as the value was closer to 0.

Light Resistance Measurement

[0052] A specimen was mounted on an accelerated weathering (QUV) apparatus and irradiated with ultraviolet (UV) light for 200 hours by the method of ASTM 4329-13, and changes in color were then calculated by using a reflectometer.

Heat Resistance Measurement

[0053] A degree of discoloration of the initial specimen according to the volatile loss measurement method and the specimen after the volatile loss test was measured. The measurement value was determined by changes in E value with respect to L,a,b values using a colorimeter.

Experimental Example 1: DOTP-based Plasticizer Compositions

1. Mixed Plasticizer Composition of DOTP and TBC

[0054] DOTP and TBC were mixed in mixing ratios of Examples 1-1 to 1-5 listed in Table 1 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens.

[0055] With reference to ASTM D638, the specimens were prepared in such a manner that 40 parts by weight of the mixed plasticizer composition, 2.5 parts by weight of an auxiliary stabilizer (ESO), and 3 parts by weight of a stabilizer (LOX-430) were mixed with 100 parts by weight of PVC in a 3 L super mixer at 700 rpm and a temperature of 98°C, a 5 mm thick sheet was prepared by using a roll mill at 160°C for 4 minutes, and a sheet having a thickness of 1 mm to 3 mm was then prepared by low-pressure pressing for 2.5 minutes and high-pressure pressing for 2 minutes at a temperature of 180°C. Physical properties of each specimen were evaluated for the above-described test items, and the results thereof are summarized in Table 6 below.

[Table 6]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)	Absorption time (sec)	Stress test (24hrs)
Example 1-1	95:5	86.5	222.6	321.7	0.20	2.32	2.14	392	0.5
Example 1-2	7:3	86.0	221.3	315.5	0.23	2.88	1.76	372	0.5
Example 1-3	5:5	84.8	216.5	313.2	0.24	2.90	1.35	341	0.5
Example 1-4	3:7	83.9	198.3	280.2	2.21	11.01	1.22	235	0.5
Example 1-5	1:9	83.1	190.3	278.5	2.45	12.31	1.19	214	0.5
Comparative Example 1	DOP	88.2	203.4	289.6	3.56	6.64	1.13	408	1.0
Comparative Example 2	DOTP	89.4	222.1	324.9	0.25	2.75	2.71	465	3.0

[0056] As illustrated in Table 6, when Examples 1-1 to 1-5 and Comparative Examples 1 and 2 using DOP and DOTP plasticizers, as commercial products widely sold, were compared, it may be confirmed that Examples 1-1 to 1-5 had all physical properties, such as hardness, absorption time, tensile strength, elongation rate, stress resistance, and migration, equal to or better than Comparative Examples 1 and 2. Furthermore, it may be understood that Examples 1-1 to 1-5 improved poor physical properties of the conventional plasticizer products.

[0057] In a case in which the absorption time of the plasticizer was short, processability may be improved. However, since limitations due to gelling may occur during processing even in the case that the absorption time is excessively short, an appropriate absorption time may need to be maintained. From this point of view, with respect to Examples 1-4 and 1-5 in which an excessive amount of TBC was mixed, the absorption time seemed to be relatively short, and thus, there is a possibility that the limitations due to gelling may occur during processing when the plasticizer composition was used. However, with respect to Examples 1-1 to 1-3 in which the amount of TBC was appropriately adjusted, since absorption was performed for an appropriate period of time, it was confirmed that the limitations did not occur. Furthermore, it may be confirmed that a difference in the physical properties, such as volatile loss, was large according to the adjustment of the mixing ratio. Thus, it may be understood that a better plasticizer composition may be obtained when the mixing ratio was appropriately adjusted.

2. Mixed Plasticizer Composition of DOTP and TOC

[0058] DOTP and TOC were mixed in mixing ratios of Examples 2-1 to 2-5 listed in Table 1 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The preparation of the specimens and physical property evaluation were performed in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC], and the results thereof are presented in Table 7 below.

[Table 7]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)	Absorption time (sec)	Stress test (24hrs)
Example 2-1	95:5	89.4	230.8	326.8	0.15	0.77	2.23	450	0.5
Example 2-2	7:3	89.5	231.6	328.1	0.13	0.60	1.90	475	0
Example 2-3	5:5	89.7	235.9	332.5	0.10	0.32	1.45	482	0
Example 2-4	3:7	91.2	235.5	340.2	0.11	0.31	1.33	586	0
Example 2-5	1:9	91.6	237.0	342.1	0.10	0.28	1.18	604	0
Comparative Example 1	DOP	88.4	205.8	282.3	3.77	6.80	1.13	420	1.0
Comparative Example 2	DOTP	89.4	226.0	320.0	0.23	2.05	2.71	445	3.0

[0059] As illustrated in Table 7, when Examples 2-1 to 2-5 and Comparative Examples 1 and 2 using DOP and DOTP plasticizers, as commercial products widely sold, were compared, it may be confirmed that Examples 2-1 to 2-5 had all physical properties equal to or better than the conventional DOTP product. Furthermore, it may be understood that Examples 2-1 to 2-5 improved poor physical properties of the conventional plasticizer products.

[0060] With respect to the absorption time, it may be understood that Examples 2-1 to 2-3 had an appropriate absorption time, but Examples 2-4 and 2-5 required a relatively long absorption time. Since this may cause the deterioration of processability and productivity, it may also be confirmed that, in some cases, it needs to be careful when an excessive amount of TOC was mixed.

3. Mixed Plasticizer Composition of DOTP and TPC

[0061] DOTP and tripentyl citrate (TPC) or triamyl citrate were mixed in mixing ratios of Examples 3-1 to 3-3 listed in Table 1 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that a stabilizer, BZ153T, was used during the formulation of the sheet, physical properties were similarly evaluated, and the results thereof are presented in Table 8 below.

[Table 8]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)	Stress test (7 days)
Example 3-1	9:1	90.6	225.3	326.1	1.57	0.70	2.30	1.0
Example 3-2	7:3	89.8	223.4	324.9	1.37	0.92	1.68	0
Example 3-3	5:5	88.7	220.0	320.4	1.09	1.08	1.12	0
Comparative Example 1	DOP	88.4	205.8	282.3	3.77	6.80	1.13	1.0
Comparative Example 2	DOTP	91.8	226.3	318.2	1.65	0.76	2.56	2.0

[0062] As illustrated in Table 8, when Examples 3-1 to 3-3 and Comparative Examples 1 and 2 using DOP and DOTP plasticizers, as commercial products widely sold, were compared, it may be confirmed that Examples 3-1 to 3-3 had all physical properties equal to or better than the conventional DOTP product. Furthermore, it may be understood that Examples 3-1 to 3-3 improved poor physical properties of the conventional plasticizer products.

4. Mixed Plasticizer Composition of DOTP and THC

[0063] DOTP and trihexyl citrate (THC) were mixed in mixing ratios of Examples 4-1 to 4-3 listed in Table 1 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that a stabilizer, BZ153T, was used during the formulation of the sheet, physical properties were similarly evaluated, and the results thereof are presented in Table 9 below.

[Table 9]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)	Stress test (7 days)
Example 4-1	9:1	91.1	221.9	319.8	0.98	0.69	2.35	1.0
Example 4-2	7:3	90.4	217.4	315.1	0.75	0.74	1.77	1.0
Example 4-3	5:5	89.9	210.6	311.5	0.62	0.73	1.23	0.5
Comparative Example 1	DOP	88.4	205.8	282.3	3.77	6.80	1.13	1.0
Comparative Example 2	DOTP	91.8	226.3	318.2	1.65	0.76	2.56	2.0

[0064] As illustrated in Table 9, when Examples 4-1 to 4-3 and Comparative Examples 1 and 2 using DOP and DOTP plasticizers, as commercial products widely sold, were compared, it may be confirmed that Examples 4-1 to 4-3 had all physical properties equal to or better than the conventional DOTP product. Furthermore, it may be understood that Examples 4-1 to 4-3 improved poor physical properties of the conventional plasticizer products.

5. Mixed Plasticizer Composition of DOTP and TiBC

[0065] DOTP and triisobutyl citrate (TiBC) were mixed in mixing ratios of Examples 5-1 to 5-4 listed in Table 1 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The preparation of the specimens and physical property evaluation were performed in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that the working temperature during the evaluation of the volatile loss was set to 100°C, and the results thereof are presented in Table 10 below.

[Table 10]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)
Example 5-1	8:2	86.0	228.6	311.2	0.82	2.35
Example 5-2	6:4	85.4	221.3	308.5	1.02	4.62
Example 5-3	4:6	84.0	217.9	302.5	1.37	6.88
Example 5-4	2:8	83.0	211.6	294.6	1.88	7.85
Comparative Example 2	DOTP	89.6	230.7	315.7	0.70	0.84
Comparative Example 3	TiBC	82.5	200.3	282.5	3.56	11.57

[0066] As illustrated in Table 10, when Examples 5-1 to 5-4 and Comparative Example 2 using a DOTP plasticizer, as a commercial product widely sold, were compared, it may be confirmed that Examples 5-1 to 5-4 had all physical properties equal to or better than the conventional DOTP product. Furthermore, it may be understood that Examples 5-1 to 5-4 improved poor physical properties of the conventional plasticizer product.

[0067] With respect to Examples 5-3 and 5-4 in which a relatively excessive amount of TiBC was included in comparison to Examples 5-1 and 5-2, it may be confirmed that tensile strength and elongation rate were reduced and migration loss and volatile loss were significantly reduced. That is, it may also be confirmed that, in some cases, it needs to be careful when an excessive amount of TiBC was mixed.

6. Mixed Plasticizer Composition of DOTP and TiNC

[0068] DOTP and triisononyl citrate (TiNC) were mixed in mixing ratios of Examples 6-1 to 6-5 listed in Table 1 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that a stabilizer, BZ153T, was used during the formulation of the sheet, physical properties were similarly evaluated, and the results thereof are presented in Table 11 below.

[Table 11]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)
Example 6-1	9:1	92.2	238.0	326.9	1.04	0.56	1.95
Example 6-2	7:3	92.5	244.8	335.5	0.85	0.48	1.68
Example 6-3	5:5	92.8	249.2	346.6	0.62	0.42	1.39
Example 6-4	3:7	94.1	257.5	360.3	0.54	0.50	1.02
Example 6-5	1:9	94.8	261.4	369.3	0.58	0.43	0.88
Comparative Example 2	DOTP	92.0	227.5	315.1	1.51	0.79	2.71

[0069] As illustrated in Table 11, when Examples 6-1 to 6-4 and Comparative Example 2 using a DOTP plasticizer, as a commercial product widely sold, were compared, it may be confirmed that Examples 6-1 to 6-4 had all physical properties equal to or better than the conventional DOTP product. Furthermore, it may be understood that Examples 6-1 to 6-4 improved poor physical properties of the conventional plasticizer product.

[0070] With respect to Examples 6-3 and 6-4 in which a relatively excessive amount of TiNC was included in comparison to Examples 6-1 and 6-2, it may be confirmed that plasticizing efficiency was reduced as hardness was significantly increased. That is, it may also be confirmed that, in some cases, it needs to be careful when an excessive amount of TiNC was mixed.

7. Mixed Plasticizer Composition of DOTP and BOC

[0071] DOTP and butyloctyl citrate (BOC) were mixed in mixing ratios of Examples 7-1 to 7-3 (BOC-A) and Examples 8-1 to 8-3 (BOC-B) listed in Table 1 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that a stabilizer, BZ153T, was used during the formulation of the sheet, physical properties were similarly evaluated, and the results thereof are presented in Table 12 below.

[Table 12]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)
Example 7-1	85:15	88.3	228.0	334.7	0.22	0.85
Example 7-2	7:3	88.0	222.6	331.6	0.18	0.42
Example 7-3	6:4	87.9	225.5	336.4	0.15	0.35
Example 8-1	85:15	88.2	222.8	332.7	0.20	0.59
Example 8-2	7:3	88.7	225.8	338.6	0.16	0.46
Example 8-3	6:4	89.8	229.7	339.4	0.12	0.32
Comparative Example 2	DOTP	89.5	228.8	318.1	0.24	1.08

[0072] As illustrated in Table 12, when Examples 7-1 to 7-3, Examples 8-1 to 8-3, and Comparative Example 2 using a DOTP plasticizer, as a commercial product widely sold, were compared, it may be confirmed that Examples 7-1 to 7-3 and Examples 8-1 to 8-3 had all physical properties equal to or better than the conventional DOTP product. In particular, it may be understood that elongation rate and volatile loss characteristics were significantly improved.

Experimental Example 2: DINTP-based Plasticizer Compositions

1. Mixed Plasticizer Composition of DINTP and TBC

[0073] DINTP and tributyl citrate (TBC) were mixed in mixing ratios of Examples 9-1 to 9-4 listed in Table 2 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that a stabilizer, BZ153T, was used during the formulation of the sheet, physical properties were similarly evaluated, and the results thereof are presented in Table 13 below.

[Table 13]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)	Stress test (24 hrs)
Example 9-1	8:2	91.0	232.1	342.0	2.38	1.03	1.74	1.5
Example 9-2	6:4	89.3	232.8	335.7	2.30	1.23	1.56	1.0
Example 9-3	4:6	87.7	225.0	316.2	2.30	1.88	1.31	0.5
Example 9-4	2:8	87.0	215.3	317.2	2.39	2.56	1.30	0.5
Comparative Example 4	DINTP	92.7	230.2	314.4	2.72	0.89	3.56	2.5
Comparative Example 5	TBC	86.3	202.4	301.4	6.99	15.38	1.33	0

[0074] As illustrated in Table 13, when Examples 9-1 to 9-4, Comparative Example 4 using a DINTP plasticizer, as a commercial product widely sold, and Comparative Example 5, in which a terephthalate-based material was not included, were compared, it may be confirmed that Examples 9-1 to 9-4 had all physical properties equal to or better than the conventional DINTP product. Furthermore, it may be understood that Examples 9-1 to 9-4 improved poor physical properties of the conventional plasticizer products.

[0075] With respect to Examples 9-3 and 9-4 in which a relatively excessive amount of TBC was included in comparison to Examples 9-1 and 9-2, it may be confirmed that effects of improving tensile strength and elongation rate were insignificant. That is, it may also be confirmed that, in some cases, it needs to be careful when an excessive amount of TBC was mixed.

2. Mixed Plasticizer Composition of DINTP and TOC

[0076] DINTP and trioctyl citrate (TOC) were mixed in mixing ratios of Examples 10-1 to 10-4 listed in Table 2 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that a stabilizer, BZ153T, was used during the formulation of the sheet and the working temperature during the evaluation of the volatile loss was set to 100°C, and the results thereof are presented in Table 14 below.

[Table 14]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)	Stress test (24 hrs)
Example 10-1	8:2	92.0	231.9	374.5	1.82	0.83	1.89	1.5
Example 10-2	6:4	91.7	229.8	369.9	1.61	0.81	1.75	1.0
Example 10-3	4:6	91.5	228.1	370.3	1.41	0.80	1.45	0.5
Example 10-4	2:8	91.3	230.2	373.4	1.24	0.81	1.46	0.5
Comparative Example 4	DINTP	92.3	217.0	341.3	2.82	1.36	3.56	2.0
Comparative Example 6	TOC	91.3	230.1	369.0	0.82	0.82	1.35	0.5

[0077] As illustrated in Table 14, when Examples 10-1 to 10-4, Comparative Example 4 using a DINTP plasticizer, as a commercial product widely sold, and Comparative Example 6, in which a terephthalate-based material was not included, were compared, it may be confirmed that Examples 10-1 to 10-4 had all physical properties equal to or better than the conventional DINTP product. Furthermore, it may be understood that Examples 10-1 to 10-4 improved poor physical properties of the conventional plasticizer product.

3. Mixed Plasticizer Composition of DINTP and TiBC

[0078] DINTP and triisobutyl citrate (TiBC) were mixed in mixing ratios of Examples 11-1 to 11-4 listed in Table 2 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that a stabilizer, BZ153T, was used during the formulation of the sheet and the working temperature during the evaluation of the volatile loss was set to 100°C, and the results thereof are presented in Table 15 below.

[Table 15]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)
Example 11-1	8:2	90.8	236.1	348.5	2.12	1.83	1.82
Example 11-2	6:4	89.5	237.5	332.8	2.00	2.11	1.46
Example 11-3	4:6	87.3	228.9	320.9	2.86	2.59	1.25
Example 11-4	2:8	87.1	221.0	315.1	3.26	3.44	1.11
Comparative Example 4	DINTP	92.5	235.7	318.7	2.99	0.89	3.56
Comparative Example 7	TiBC	86.0	210.3	296.7	7.56	14.23	1.09

[0079] As illustrated in Table 15, when Examples 11-1 to 11-4, Comparative Example 4 using a DINTP plasticizer, as a commercial product widely sold, and Comparative Example 7, in which a terephthalate-based material was not included, were compared, it may be confirmed that Examples 11-1 to 11-4 had all physical properties equal to or better than the conventional DINTP product. Furthermore, it may be understood that Examples 11-1 to 11-4 improved poor physical properties of the conventional plasticizer products.

[0080] With respect to Examples 11-3 and 11-4 in which a relatively excessive amount of TiBC was included in comparison to Examples 11-1 and 11-2, it may be confirmed that effects of improving tensile strength and elongation rate characteristics were insignificant. That is, it may also be confirmed that, in some cases, it needs to be careful when an excessive amount of TiBC was mixed.

Experimental Example 3: Mixed Plasticizer Compositions of First Mixture and BOC

[0081] The first mixture (DOTP/BOTP/DBTP) of Preparation Example 3 and butyloctyl citrate (BOC) were mixed in mixing ratios of Examples 12-1 to 12-3 (BOC-A) and Examples 13-1 to 13-3 (BOC-B) listed in Table 3 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that 50 parts by weight of the mixed plasticizer composition was added, an auxiliary stabilizer (ESO) was not added, and a stabilizer, BZ153T, was used during the formulation of the sheet, physical properties were similarly evaluated, and the results thereof are presented in Tables 16 and 17 below.

[Table 16]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)
Example 12-1	85:15	82.3	208.04	344.68	3.94	1.62
Example 12-2	7:3	81.0	202.56	341.64	3.69	1.42
Example 12-3	6:4	80.9	205.51	346.35	3.21	1.28
Example 13-1	85:15	81.2	202.84	342.71	3.71	1.59
Example 13-2	7:3	81.7	205.76	348.63	3.32	1.36
Example 13-3	6:4	82.8	209.66	348.12	2.90	1.19
Comparative Example 8	First mixture	81.8	212.82	349.42	4.24	1.79

[Table 17]

Stress test	24 hours	72 hours	168 hours
Example 12-1	1.0	1.5	2.0
Example 12-2	1.0	0.5	2.0
Example 12-3	0.5	1.0	1.5
Example 13-1	1.0	1.5	2.0
Example 13-2	1.0	1.0	1.5
Example 13-3	1.0	1.5	1.5
Comparative Example 8	1.5	2.0	2.5

[0082] As illustrated in Tables 16 and 17, when Examples 12-1 to 12-3, Examples 13-1 to 13-3, and Comparative Example 8 using the mixed plasticizer composition, as a mixed composition of DOTP, BOTP, and DBTP, were compared, it may be confirmed that Examples 12-1 to 12-3 and Examples 13-1 to 13-3 had all physical properties equal to or better than the conventional product.

Experimental Example 4: Mixed Plasticizer Compositions of Third Mixture and TBC or TOC

[0083] The third mixture (DINTP/OINTP/DOTP) of Preparation Example 4 and tributyl citrate (TBC) or trioctyl citrate (TOC) were mixed in mixing ratios of Examples 14-1 to 14-4 and Example 15-1 listed in Table 4 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The preparation of the specimens and physical property evaluation were performed in the same manner as before, and the results thereof are presented in Tables 18 and 19 below.

[Table 18]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)	Light resistance (E)
Example 14-1	95:5	92.0	254.5	308.2	1.90	0.73	3.21
Example 14-2	7:3	91.1	246.0	303.6	1.71	0.85	2.85
Example 14-3	5:5	88.2	241.0	297.0	1.63	0.93	2.12
Example 14-4	1:9	86.5	216.3	264.6	1.68	2.12	2.01
Example 15-1	7:3	92.5	257.5	299.3	1.48	0.65	2.94
Comparative Example 2	DOTP	91.6	246.4	296.6	1.68	0.72	5.67
Comparative Example 9	Third mixture	92.8	254.4	309.0	2.03	0.72	5.23

[Table 19]

Stress test	24 hours	72 hours	168 hours
Example 14-1	0.5	1.5	1.5
Example 14-2	0	0.5	1.0
Example 14-3	0	0.5	0
Example 14-4	0	0	0
Example 15-1	0.5	1.0	1.5
Comparative Example 2	0.5	1.0	1.5
Comparative Example 9	0.5	1.5	1.5

[0084] As illustrated in Tables 18 and 19, when Examples 14-1 to 14-4, Example 15-1, and Comparative Example 9 using the mixed plasticizer composition, as a mixed composition of DINTP, OINTP, and DOTP, were compared, it may be confirmed that Examples 14-1 to 14-4 and Example 15-1 had all physical properties equal to or better than the conventional product.

[0085] With respect to Example 14-4 in which a relatively excessive amount of TBC was included in comparison to Examples 14-1 to 14-3, it may be confirmed that tensile strength and elongation rate characteristics were reduced and volatile loss was also poor. That is, it may also be confirmed that, in some cases, it needs to be careful when an excessive amount of TBC was mixed.

Experimental Example 5: Mixed Plasticizer Compositions of DOTP, TBC, and Epoxidized Oil

1. Mixed Plasticizer Composition of DOTP, TBC, and ESO

[0086] DOTP, TBC, and ESO were mixed in mixing ratios of Examples 16-1 to 16-5 listed in Table 5 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens. The specimens were prepared in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that 30 parts by weight of the mixed plasticizer composition was added, an auxiliary stabilizer (ESO) was not added, and 0.5 part by weight of titanium dioxide (TiO₂) was additionally used during the formulation of the sheet, physical properties were similarly evaluated and the results thereof are presented in Table 20 below, and the results of the heat resistance test are presented in FIGS. 1 and 2.

[Table 20]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)
Example 1-2	7:3	94.2	246.7	300.8	0.92	1.57
Example 16-1	3:5:2	93.0	247.8	313.9	0.59	1.55
Example 16-2	6:3:1	94.0	252.5	322.3	0.68	1.14
Example 16-3	6:2:2	94.3	252.5	322.2	0.62	0.80
Example 16-4	5:3:2	94.0	247.9	310.1	0.64	1.00
Example 16-5	4:4:2	93.5	243.2	316.4	0.53	1.17
Comparative Example 2	DOTP	95 .5	268.5	311.0	0.78	0.61

[0087] As illustrated in Table 20, when Examples 16-1 to 16-5 and Comparative Example 2, the DOTP plasticizer composition as a conventionally used product, were compared, it may be confirmed that the plasticizer compositions of the examples had properties equal to or better than the conventional product.

[0088] Referring to images of FIGS. 1 and 2 as the results of the heat resistance test, it may be confirmed that since Example 1-2, in which epoxidized oil was not added, was vulnerable to heat, it was blackened. However, it may be confirmed that there was no change when a predetermined amount of the epoxidized oil was added. That is, in a case in which a Citrate-based material was added to improve physical properties of DOTP as a conventional product, it may be confirmed that heat resistance characteristics may be relatively poor, but even the heat resistance was also maintained and improved when the epoxidized oil was added at the same time.

2. Mixed Plasticizer Composition of DOTP, TOC, and ESO

[0089] DOTP, TOC, and ESO were mixed in mixing ratios of Examples 17-1 to 17-3 listed in Table 5 to obtain mixed plasticizer compositions, and the compositions were used as experimental specimens.

[0090] With reference to ASTM D638, the specimens were prepared in such a manner that 50 parts by weight of the mixed plasticizer composition, 40 parts by weight of a filler (OMYA1T), 5 parts by weight of a stabilizer (RUP-144), and 0.3 part by weight of a lubricant (St-A) were mixed with 100 parts by weight of PVC in a 3 L super mixer at 700 rpm and a temperature of 98°C, a 5 mm thick sheet was prepared by using a roll mill at 160°C for 4 minutes, and a sheet having a thickness of 1 mm to 3 mm was then prepared by low-pressure pressing for 2.5 minutes and high-pressure pressing for 2 minutes at a temperature of 180°C.

[0091] Physical properties of each specimen were evaluated for the above-described test items, and the specimens were evaluated in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC] except that the working temperature was set to 121°C and the evaluation was carried out for 168 hours during the volatile loss measurement. The following items were additionally evaluated and the results thereof are presented in Tables 21 and 22 below, and the results of the heat resistance test are presented in FIG. 3.

<Additional Test Items>

Residual Tensile Strength

[0092] The measurement was performed in the same manner as the above-described tensile strength measurement, and specimens exposed at 121°C for 168 hours were used.

Residual Elongation

[0093] The measurement was performed in the same manner as the above-described elongation rate measurement, and specimens exposed at 121°C for 168 hours were used.

Low temperature Resistance

[0094] Five prepared specimens were left standing at a specific temperature for 3 minutes and were then hit. The temperature was measured when three out of the five specimens were broken.

[Table 21]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Residual tensile strength (%)	Elongation rate (%)	Residual elongation (%)	Migration loss (%)	Volatile loss (%)	Low temperature resistance (°C)	Heat resistance (E)
Example 17-1	3:3:4	86.8	184.3	96.4	292.6	89.5	0.48	8.63	-24.0	35.53
Example 17-2	4:3:3	87.0	185.3	96.5	297.8	92.5	0.63	7.04	-24.5	31.46
Example 17-3	5:3:2	86.8	183.0	103.7	314.8	93.9	0.91	7.06	-26.0	51.13
Comparative Example 10	DIDP	87.5	175.6	94.5	317.9	91.3	0.99	8.36	-25.5	49.18
Comparative Example 11	DINIP	88.0	181.3	94.9	310.2	89.5	1.60	10.49	-28.5	47.02

[0095] As illustrated in Table 21, when Examples 17-1 to 17-3 and Comparative Examples 10 and 11, the DIDP and DINIP plasticizer compositions as conventionally used products, were compared, it may be confirmed that the plasticizer compositions of the examples had properties equal to or better than the conventional products. In particular, it may be confirmed that low temperature resistance properties were almost the same as those of the conventional products, but heat resistance properties were significantly improved.

[0096] Referring to an image of FIG. 3 as the results of the thermal stability test, it may be confirmed that since Comparative Examples 10 and 11, as the conventional products, were vulnerable to heat, Comparative Examples 10 and 11 were blackened. However, it may be confirmed that there was no change when a predetermined amount of epoxidized oil was added. That is, in a case in which the epoxidized oil as well as a Citrate-based material was added to improve physical properties of the conventional plasticizer products such as DIDP and DINIP, it was confirmed that even the thermal stability may also be maintained and improved.

Experimental Example 6: Comparison to Acetyl Citrate-based Material

[0097] In order to compare differences in physical properties between a case, in which an acetyl group was included in the Citrate-based material, and a case in which an acetyl group was not included in the Citrate-based material, Examples 1-2, 2-2, and 5-2 and Comparative Example 12, a plasticizer composition in which acetyl 2-ethylhexyl citrate and DOTP were mixed, were used as experimental specimens. The preparation of the specimens and physical property evaluation were performed in the same manner as in [1. Mixed Plasticizer Composition of DOTP and TBC], and the results thereof are presented in Table 22 below.

[Table 22]

	Plasticizer	Hardness (Shore "A")	Tensile strength (Kg/cm2)	Elongation rate (%)	Migration loss (%)	Volatile loss (%)
Example 1-2	DOTP+TBC (70:30)	86.0	221.3	315.5	0.23	2.88
Example 2-2	DOTP+TOC (70:30)	89.5	231.6	328.1	0.13	0.60
Example 5-2	DOTP+TiBC (60:40)	85.4	221.3	308.5	1.02	4.62
Comparative Example 12	DOTP+ATOC (70:30)	91.2	237.9	284.6	0.25	0.54

[0098] As illustrated in Table 22, in a case in which acetyl 2-ethylhexyl citrate was mixed and used, it may be confirmed that since hardness was significantly increased, plasticizing efficiency, as a physical property highly required for a plasticizer product, may be deteriorated and elongation rate characteristics were also reduced. Accordingly, since economic and process losses may secondarily occur due to the fact that more plasticizer was needed in comparison to other products, it may be understood that, in some cases, it may adversely affect the quality of the product according to the presence of the acetyl group.

Claims

1. A plasticizer composition comprising:

a terephthalate-based material; and

a Citrate-based material,

wherein a weight ratio of the terephthalate-based material to the Citrate-based material is in a range of 8:2 to 6:4,

wherein the Citrate-based material is one in which an acetyl group is not included, and

wherein the terephthalate-based material and the Citrate-based material are, respectively,

(a) di(2-ethylhexyl)terephthalate (DEHTP or DOTP) and triisobutyl citrate (TiBC), or

(b) diisononyl terephthalate (DINTP) and tributyl citrate (TBC), or

(c) diisononyl terephthalate (DINTP) and triisobutyl citrate (TiBC).

2. The plasticizer composition of claim 1, further comprising an epoxidized oil.

3. The plasticizer composition of claim 2, wherein the epoxidized oil is included in an amount of 1 parts by weight to 100 parts by weight based on 100 parts by weight of the plasticizer composition.

4. The plasticizer composition of claim 2, wherein the epoxidized oil comprises at least one selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid ester, epoxidized oleic acid ester, epoxidized tall oil, and epoxidized linoleic acid ester.

5. A method of preparing a plasticizer composition, the method comprising:

preparing a terephthalate-based material and a Citrate-based material; and

obtaining a plasticizer composition by blending the terephthalate-based material and the Citrate-based material in a weight ratio of 8:2 to 6:4,

wherein the Citrate-based material is one in which an acetyl group is not included, and

wherein the terephthalate-based material and the Citrate-based material are, respectively,

(a) di(2-ethylhexyl)terephthalate (DEHTP or DOTP) and triisobutyl citrate (TiBC), or

(b) diisononyl terephthalate (DINTP) and tributyl citrate (TBC), or

(c) diisononyl terephthalate (DINTP) and triisobutyl citrate (TiBC).

6. A resin composition comprising:

100 parts by weight of a resin; and

5 parts by weight to 150 parts by weight of the plasticizer composition of claim 1.

7. The resin composition of claim 6, wherein the resin comprises at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and a thermoplastic elastomer.

8. The resin composition of claim 6, wherein the resin composition is a material of at least one product selected from the group consisting of electric wires, flooring materials, automotive interior materials, films, sheets, wallpaper, and tubes.

Ansprüche

1. Weichmacherzusammensetzung, umfassend:

ein Material auf Terephthalatbasis; und

ein Material auf Citratbasis,

wobei ein Gewichtsverhältnis des Materials auf Terephthalatbasis zum Material auf Citratbasis in einem Bereich von 8:2 bis 6:4 ist,

wobei das Material auf Citratbasis eines ist, in welchem eine Acetylgruppe nicht eingeschlossen ist, und

wobei das Material auf Terephthalatbasis bzw. das Material auf Citratbasis sind

(a) Di(2-ethylhexyl)terephthalat (DEHTP oder DOTP) und Triisobutylcitrat (TiBC), oder

(b) Diisononylterephthalat (DINTP) und Tributylcitrat (TBC), oder

(c) Diisononylterephthalat (DINTP) und Triisobutylcitrat (TiBC).

2. Weichmacherzusammensetzung nach Anspruch 1, weiter umfassend ein epoxidiertes Öl.

3. Weichmacherzusammensetzung nach Anspruch 2, wobei das epoxidierte Öl in einer Menge von 1 Gewichtsteil bis 100 Gewichtsteilen, basierend auf 100 Gewichtsteilen der Weichmacherzusammensetzung, eingeschlossen ist.

4. Weichmacherzusammensetzung nach Anspruch 2, wobei das epoxidierte Öl wenigstens eines umfasst, ausgewählt aus der Gruppe bestehend aus epoxidiertem Sojabohnenöl, epoxidiertem Kastoröl, epoxidiertem Leinsamenöl, epoxidiertem Palmöl, epoxidiertem Stearinsäureester, epoxidiertem Ölsäureester, epoxidiertem Tallöl und epoxidiertem Linolsäureester.

5. Verfahren zum Herstellen einer Weichmacherzusammensetzung, wobei das Verfahren umfasst:

Herstellen eines Materials auf Terephthalatbasis und eines Materials auf Citratbasis; und

Erhalten einer Weichmacherzusammensetzung durch Mischen des Materials auf Terephthalatbasis und des Materials auf Citratbasis in einem Gewichtsverhältnis von 8:2 bis 6:4,

wobei das Material auf Citratbasis eines ist, in welchem eine Acetylgruppe nicht eingeschlossen ist, und

wobei das Material auf Terephthalatbasis bzw. das Material auf Citratbasis sind

(a) Di(2-ethylhexyl)terephthalat (DEHTP oder DOTP) und Triisobutylcitrat (TiBC), oder

(b) Diisononylterephthalat (DINTP) und Tributylcitrat (TBC), oder

(c) Diisononylterephthalat (DINTP) und Triisobutylcitrat (TiBC).

6. Harzzusammensetzung, umfassend:

100 Gewichtsteile eines Harzes;

5 Gewichtsteile bis 150 Gewichtsteile der Weichmacherzusammensetzung nach Anspruch 1.

7. Harzzusammensetzung nach Anspruch 6, wobei das Harz wenigstens eines umfasst, ausgewählt aus der Gruppe bestehend aus Ethylenvinylacetat, Polyethylen, Polypropylen, Polyvinylchlorid, Polystyrol, Polyurethan und einem thermoplastischen Elastomer.

8. Harzzusammensetzung nach Anspruch 6, wobei die Harzzusammensetzung ein Material wenigstens eines Produkts ist, ausgewählt aus der Gruppe bestehend aus elektrischen Drähten, Bodenmaterialien, Automobilinnenraummaterialien, Folien, Bögen, Tapete und Röhren.

Revendications

1. Composition de plastifiant comprenant :

un matériau à base de téréphtalate ; et

un matériau à base de citrate.

dans laquelle un rapport pondéral du matériau à base de téréphtalate au matériau à base de citrate est de l'ordre de 8 : 2 à 6:4,

dans laquelle le matériau à base de citrate est un matériau dans lequel un groupe acétyle n'est pas compris, et
dans laquelle le matériau à base de téréphtalate et le matériau à base de citrate sont, respectivement,

(a) du téréphtalate de di(2-éthylhexyle) (DEHTP ou DOTP) et du citrate de triisobutyle (TiBC), ou

(b) du téréphtalate de diisononyle (DINTP) et du citrate de tributyle (TBC), ou

(c) du téréphtalate de diisononyle (DINTP) et du citrate de triisobutyle (TiBC).

2. Composition de plastifiant selon la revendication 1, comprenant en outre de l'huile époxydée.

3. Composition de plastifiant selon la revendication 2, dans laquelle l'huile époxydée est comprise en une quantité de 1 partie en poids à 100 parties en poids par rapport à 100 parties en poids de la composition de plastifiant.

4. Composition de plastifiant selon la revendication 2, dans laquelle l'huile époxydée comprend au moins un composé sélectionné dans le groupe d'huile de soja époxydée, d'huile de ricin époxydée, d'huile de lin époxydée, d'huile de palme époxydée, d'ester d'acide stéarique époxydé, d'ester d'acide oléique époxydé, d'huile de tall époxydée et d'ester d'acide linoléique époxydé.

5. Procédé de préparation d'une composition de plastifiant, le procédé comprenant les étapes consistant à :

préparer un matériau à base de téréphtalate et un matériau à base de citrate ; et

obtenir une composition de plastifiant en mélangeant le matériau à base de téréphtalate et le matériau à base de citrate dans un rapport pondéral de l'ordre de 8 : 2 à 6 : 4,

dans lequel le matériau à base de citrate est un matériau dans lequel un groupe acétyle n'est pas inclus, et

dans lequel le matériau à base de téréphtalate et le matériau à base de citrate sont, respectivement,

(a) du téréphtalate de di(2-éthylhexyle) (DEHTP ou DOTP) et du citrate de triisobutyle (TiBC), ou

(b) du téréphtalate de diisononyle (DINTP) et du citrate de tributyle (TBC), ou

(c) du téréphtalate de diisononyle (DINTP) et du citrate de triisobutyle (TiBC).

6. Composition de résine comprenant :

100 parties en poids d'une résine ; et

5 parties en poids à 150 parties en poids de la composition de plastifiant selon la revendication 1.

7. Composition de résine selon la revendication 6, dans laquelle la résine comprend au moins un composé sélectionné dans le groupe constitué d'éthylène-acétate de vinyle, de polyéthylène, de polypropylène, de chlorure de polyvinyle, de polystyrène, de polyuréthane et d'un élastomère thermoplastique.

8. Composition de résine selon la revendication 6, dans laquelle la composition de résine est un matériau d'au moins un produit sélectionné dans le groupe constitué de fils électriques, de matériaux de revêtement de sol, de matériaux intérieurs automobiles, de films, de feuilles, de papier peint et de tubes.

Drawing